Supported hybrid metallocene catalyst, method for preparing the same, and method for preparing polyolefin using the same

Abstract

The present invention relates to a supported metallocene catalyst used for preparing polyolefin whose physical properties and molecular weight distribution can be easily controlled, a method for preparing the same, and a method for preparing polyolefin using the same, more particularly to a support metallocene catalyst wherein at least two kinds of metallocenic transition compounds are supported on a metal oxide such as silica, a method for preparing the same, and a method for preparing polyolefin using the same.

1. A supported hybrid metallocene catalyst with at least two different metallocene compounds supported on a single support, wherein:
 at least one metallocene compound is supported on the support by a chemical bond of its ligand to the support surface; and 
 the other metallocene compound is supported on the support by a chemical bond of its ligand to a cocatalyst chemically bonded to the support surface. 
 
     
     
       2. The supported hybrid metallocene catalyst according to  claim 1 , wherein said at least one metallocene compound is a catalyst for preparing low molecular weight polyolefin and the other is a catalyst for preparing high molecular weight polyolefin. 
     
     
       3. The supported hybrid metallocene catalyst according to  claim 2 , wherein the low molecular weight polyolefin has a molecular weight ranging from 1,000 to 100,000, and the high molecular weight polyolefin has a molecular weight higher than that of the low molecular weight polyolefin, ranging from 10,000 to 1,000,000. 
     
     
       4. The supported hybrid metallocene catalyst according to  claim 1 , wherein the supporting amount of the metallocene compounds is 0.1 to 20 wt % of the total supported hybrid metallocene catalyst weight, based on the weight of metals comprised in each metallocene compound. 
     
     
       5. The supported hybrid metallocene catalyst according to  claim 1 , wherein the supporting amount of said at least one metallocene compound is 0.01 to 100 mol for 1 mol of the other metallocene compound. 
     
     
       6. The supported hybrid metallocene catalyst according to  claim 1 , wherein the supported hybrid metallocene catalyst is further supported 1 to 10,000 mol of a cocatalyst component for polyolefin polymerization per 1 mol of metals comprised in the metallocene compound, based on the metal contained in the cocatalyst. 
     
     
       7. A supported hybrid metallocene catalyst for preparing polyolefin having a bimodal or broad molecular weight distribution, which is obtained by supporting a) a catalyst component on b) a support, wherein
 a) the catalyst component comprises:
 i) a first metallocene compound having an acetal, ketal, tertiary alkoxyalkyl, benzyloxyalkyl, substituted benzyloxyalkyl, monothioacetal or monothioketal group; 
 ii) a second metallocene compound having a bridge linkage containing a Lewis base in cyclopentadiene, a cyclopentadiene derivative or a bridge group; and 
 iii) an organometallic compound containing a group XIII metal; and 
 
 b) the support has siloxane groups on the surface, on which the catalyst component is supported. 
 
     
     
       8. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the first metallocene compound is a compound represented by the following Chemical Formula 1:
   (C 5 R 1 ) p (C 5 R 2 )MQ 3−p   Chemical Formula 1 
 wherein: 
 M is a group IV transition metal; 
 each of (C 5 R 1 ) and (C 5 R 2 ) is cyclopentadienyl; cyclopentadienyl wherein two neighboring carbon atoms of C 5  are connected by a hydrocarbyl radical to form one or more C 4  to C 16  rings; or a substituted cyclopentadienyl ligand; 
 each of R 1  and R 2  is identical or different and a substituent selected from hydrogen radical, C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical; and at least one hydrogen radical comprised in the substituent of R 1  and R 2  is further substituted by a radical represented by the following Chemical Formula a, the following Chemical Formula b, or the following Chemical Formula c; 
 Q is a halogen radical; a C 1  to C 20  alkyl radical, alkenyl radical, aryl radical, alkylaryl radical, arylalkyl radical; or a C 1  to C 20  alkylidene radical; and 
 P is 0 or 1: 
 
       
         
           
           
               
               
           
         
         wherein: 
         Z is an oxygen atom or a sulfur atom; 
         each of R and R′ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl; or arylalkenyl radical; and the two R′s may be connected to form a ring; 
         G is a C 1  to C 40  alkoxy, aryloxy, alkylthio, arylthio, phenyl or substituted phenyl, and may be connected to R′ to form a ring; 
         if Z is a sulfur atom, G should be alkoxy or aryloxy; and 
         if G is alkylthio, arylthio, phenyl or substituted phenyl, Z should be an oxygen atom; 
       
       
         
           
           
               
               
           
         
         wherein 
         Z is an oxygen atom or a sulfur atom, and at least one of the two Zs is an oxygen atom; 
         each of R and R″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         R and R″ may be connected to form a ring; and 
         unless both R″s are hydrogen radicals, they may be connected to form a ring; and 
       
       
         
           
           
               
               
           
         
         wherein: 
         each of R and R′″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         two neighboring R′″s may be connected to form a ring; and 
         if at least one of Rs is a hydrogen radical, all R′″s are not hydrogen radicals, and if at least one of R′″s is a hydrogen radical, all Rs are not hydrogen radical. 
       
     
     
       9. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the first metallocene compound is [A—O—(CH 2 ) a —C 5 H 4 ] 2 ZrCl 2  or [A—O—(CH 2 ) a —C 9 H 6 ]ZrCl 3 , wherein each a is an integer of 4 to 8, and each A is methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
     
     
       10. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the first metallocene compound is one of the following compounds: 
       
         
           
           
               
               
           
         
         wherein each a is an integer 4 to 8, and each A is methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
       
     
     
       11. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the second metallocene compound is a compound represented by the following Chemical Formula 2 or Chemical Formula 3: 
       
         
           
           
               
               
           
         
         wherein: 
         M is a group IV transition metal; 
         each of (C 5 R 3 ), (C 5 R 4 ) and (C 5 R 5 ) is a cyclopentadienyl; a cyclopentadienyl wherein two neighboring carbon atoms of C 5  are connected by a hydrocarbyl radical to form one or more C 4  to C 16  ring; or a substituted cyclopentadienyl ligand; 
         each of R 3 , R 4 , and R 5  is identical or different and a substituent selected from hydrogen radical, C 1  to C 40  alkyl cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical; and at least one hydrogen radical comprised in the substituent of R 3 , R 4 , and R 5  is further substituted by a radical represented by the following Chemical Formula a, the following Chemical Formula b, the following Chemical Formula c, or the following Chemical Formula d; 
         each Q is identical or different halogen radical; C 1  to C 20  alkyl radical, alkenyl radical, aryl radical, alkylaryl radical, arylalkyl radical; or C 1  to C 20  alkylidene radical; 
         X is a bridge for binding two cyclopentadienyl ligands or a cyclopentadienyl ligand and JR 9   z−y  by a covalent bond, which is a radical having the formula of C m H 2m−1 , monoalkyl silicon, monoalkyl germanium, phosphine, or amine, wherein m is an integer of 1 to 4: 
         R 9  is a hydrogen radical, a C 1  to C 20  alkyl radical, an alkenyl radical, an aryl radical, an alkylaryl radical or an arylalkyl radical; 
         J is a group XV element or a group XVI element; 
         D is an oxygen or amine; 
         A is a hydrogen radical, a C 1  to C 20  alkyl radical, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, an alkylsilyl radical, an arylsilyl radical, methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl; and 
         a is an integer of 4 to 8: 
       
       
         
           
           
               
               
           
         
         wherein: 
         Z is an oxygen atom or a sulfur atom; 
         each of R and R′ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl; or arylalkenyl radical; and the two R′s may be connected to form a ring; 
         G is a C 1  to C 40  alkoxy, aryloxy, alkylthio, arylthio, phenyl or substituted phenyl, and may be connected to R′ to form a ring; 
         if Z is a sulfur atom, G should be alkoxy or aryloxy; and 
         if G is alkylthio, arylthio, phenyl or substituted phenyl, Z should be an oxygen atom; 
       
       
         
           
           
               
               
           
         
         wherein 
         Z is an oxygen atom or a sulfur atom, and at least one of the two Zs is an oxygen atom; 
         each of R and R″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         R and R″ may be connected to form a ring; and 
         unless both R″s are hydrogen radicals, they may be connected to form a ring; 
       
       
         
           
           
               
               
           
         
         wherein: 
         each of R and R′″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         two neighboring R′″s may be connected to form a ring; and 
         if at least one of Rs is a hydrogen radical, all R′″s are not hydrogen radicals, and if at least one of R′″s is a hydrogen radical, all Rs are not hydrogen radical; and 
       
       
         
           
           
               
               
           
         
         wherein: 
         Z is an oxygen, sulfur, nitrogen, phosphorus or arsenic atom; 
         each of R is identical or different hydrogen radical, C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         R″″ is a hydrogen radical or C 1  to C 40  alkyl, aryl, alkenyl, alkylaryl, alkylsilyl, arylsilyl, phenyl or substituted phenyl; and 
         n is 1 or 2, where if Z is oxygen or sulfur n is 1, and if Z is nitrogen, phosphorus or arsenic n is 2. 
       
     
     
       12. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the second metallocene compound is [(A—D—(CH 2 ) a )(CH 3 )X(C 5 H 4 )(9-C 13 H 9 )]ZrCl 2  or [(A—D—(CH 2 ) a )](CH 3 )X(C 5 Me 4 )(NCMe 3 )]TiCl 2 , wherein each a is an integer of 4 to 8, each X is C, CHCH or silicon, each D is an oxygen or amine, and each A is hydrogen, C 1  to C 20  alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkylsilyl, arylsilyl, methoxymethyl, t-butoxymethyl, tertrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
     
     
       13. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the second metallocene compound is one of the following compounds: 
       
         
           
           
               
               
           
         
         wherein each a is an integer of 4 to 8, each D is an oxygen or amine, and each A is a hydrogen radical, a C 1  to C 20  alkyl radical, an alkenyl radical, an aryl radical, an alkylaryl radical an arylalkyl radical, an alkylsilyl radical, an arylsilyl radical, methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
       
     
     
       14. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the cocatalyst is a compound selected from a group consisting of compounds represented by the following Chemical Formula 4, Chemical Formula 5 and Chemical Formula 6:
   [Al(R 6 )—O] n —  Chemical Formula 4 
 wherein: 
 R 6  is a C 1  to C 20  hydrocarbyl radical substituted by identical or different halogen radical, C 1  to C 20  hydrocarbyl radical or halogen; and 
 a is an integer larger than 2;
   M′(R 7 ) 3   Chemical Formula 5 
 
 wherein: 
 M′ is aluminum or boron; and 
 R 7  is a C 1  to C 20  hydrocarbyl radical substituted by identical or different halogen radical, C 1  to C 20  hydrocarbyl radical or halogen; and
   [L—H] + [M′E 4 ] −  or [L] + [M′E 4 ] −   Chemical Formula 6 
 
 wherein: 
 L is a neutral or cationic Lewis acid; 
 H is a hydrogen atom; 
 M′ is a group XIII element, such as aluminum and boron; and 
 E is a C 6  to C 40  aryl radical substituted by one or more C 1  to C 20  hydrocarbyl radicals containing a halogen radical, C 1  to C 20  hydrocarbyl, alkoxy, phenoxy radical, nitrogen, phosphorus, sulfur or oxygen atom, and the four Es may be identical or different. 
 
     
     
       15. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 14 , wherein the compound represented by Chemical Formula 4 is methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane or butylaluminoxane. 
     
     
       16. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 14 , wherein the compound represented by Chemical Formula 5 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminummethoxide, dimethylaluminumethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron or tributylboron. 
     
     
       17. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 14 , wherein the compound represented by Chemical Formula 6 is triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, trimethylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tripropylammoniumtetraphenylaluminum, trimethylammoniumtetra(p-tolyl)aluminum, tripropylammoniumtetra(p-tolyl)aluminum, triethylammoniumtetra(o,p-dimethylphenyl)aluminum, tributylammoniumtetra(p-trifluoromethylphenyl)aluminum, trimethylammoniumtetra(p-trifluoromethylphenyl)aluminum, tributylammoniumtetrapentafluorophenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetraphenylaluminum, N,N-diethylaniliniumtetrapentafluorophenylaluminum, diethylammonium tetrapentafluorophenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, triethylammoniumtetraphenylboron, tri butylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, trimethylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetrapentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenylcarboniumtetra(p-trifluoromethylphenyl)boron or triphenylcarbonium tetrapentafluorophenylboron. 
     
     
       18. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the support is dried at high temperature ranging from 300 to 1,000° C. and has highly reactive siloxane groups on the surface. 
     
     
       19. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the support is silica, silica-alumina or silica-magnesia. 
     
     
       20. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the support has 0.1 to 1 mmol/g of alcohol groups (—OH) on the surface. 
     
     
       21. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 20 , wherein the support has 0.1 to 0.5 mmol/g of alcohol groups (—OH) on the surface. 
     
     
       22. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the supporting amount of the first metallocene compound and the second metallocene compound is 0.1 to 20 wt % of the total supported hybrid metallocene catalyst weight, based on the weight of group IV metals comprised in each compound. 
     
     
       23. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the supporting amount of the cocatalyst is 1 to 10,000 mol of the group XIII metal for 1 mol of the group IV metal comprised in the second metallocene compound. 
     
     
       24. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , wherein the supporting amount of the second metallocene compound is 0.01 to 100 mol for 1 mol of the first metallocene compound. 
     
     
       25. The supported hybrid metallocene catalyst for preparing polyolefin according to  claim 7 , which has been pre-polymerized by contact with an olefinic monomer. 
     
     
       26. A method for preparing a supported hybrid metallocene catalyst for preparing polyolefin having a bimodal or broad molecular weight distribution, which comprises:
 a) a step of preparing a first supported catalyst by supporting a first metallocene compound having an acetal, ketal, tertiary alkoxyalkyl, benzyloxyalkyl, substituted benzyloxyalkyl, monothioacetal or monothioketal functional group on a support having siloxane groups on the surface; 
 b) a step of preparing an activated first supported catalyst by contacting the first supported catalyst with an organometallic compound cocatalyst containing a group XIII metal; and 
 c) a step of supporting a second metallocene compound having a bridge linkage containing at least one Lewis base in cyclopentadiene, a cyclopentadiene derivative or a bridge group on the activated first supported catalyst to prepare a supported hybrid metallocene catalyst wherein the first metallocene compound and the second metallocene compound are supported. 
 
     
     
       27. A method for preparing a supported hybrid metallocene catalyst for preparing polyolefin having a bimodal or broad molecular weight distribution, which comprises:
 a) a step of supporting a first metallocene compound having an acetal, ketal, tertiary alkoxyalkyl, benzyloxyalkyl, substituted benzyloxyalkyl, monothioacetal or monothioketal functional group on a support having siloxane groups on the surface to prepare a first supported catalyst; 
 b) a step of contacting a second metallocene compound having a bridge linkage containing at least one Lewis base in cyclopentadiene, a cyclopentadiene derivative or a bridge group with an organometallic compound cocatalyst containing a group XIII metal to prepare an activated second metallocene compound; and 
 c) a step of supporting the activated second metallocene compound on the first supported catalyst to prepare a supported hybrid metallocene catalyst wherein the first metallocene compound and the second metallocene compound are supported. 
 
     
     
       28. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the first metallocene compound is a compound represented by the following Chemical Formula 1:
   (C 5 R 1 ) p (C 5 R 2 )MQ 3−p   Chemical Formula 1 
 wherein: 
 M is a group IV transition metal; 
 each of (C 5 R 1 ) and (C 5 R 2 ) is cyclopentadienyl; cyclopentadienyl wherein two neighboring carbon atoms of C 5  are connected by a hydrocarbyl radical to form one or more C 4  to C 16  rings; or a substituted cyclopentadienyl ligand; 
 each of R 1  and R 2  is identical or different and a substituent selected from hydrogen radical, C 1  to C 40  alkyl cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical; and at least one hydrogen radical comprised in the substituent of R 1  and R 2  is further substituted by a radical represented by the following Chemical Formula a, the following Chemical Formula b, or the following Chemical Formula c; 
 Q is a halogen radical; a C 1  to C 20  alkyl radical, alkenyl radical, aryl radical, alkylaryl radical, arylalkyl radical; or a C 1  to C 20  alkylidene radical; and 
 P is 0 or 1: 
 
       
         
           
           
               
               
           
         
         wherein: 
         Z is an oxygen atom or a sulfur atom; 
         each of R and R′ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl; or arylalkenyl radical; and the two R′s may be connected to form a ring; 
         G is a C 1  to C 40  alkoxy, aryloxy, alkylthio, arylthio, phenyl or substituted phenyl, and may be connected to R′ to form a ring; 
         if Z is a sulfur atom, G should be alkoxy or aryloxy; and 
         if G is alkylthio, arylthio, phenyl or substituted phenyl, Z should be an oxygen atom; 
       
       
         
           
           
               
               
           
         
         wherein 
         Z is an oxygen atom or a sulfur atom, and at least one of the two Zs is an oxygen atom; 
         each of R and R″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         R and R″ may be connected to form a ring; and 
         unless both R″s are hydrogen radicals, they may be connected to form a ring; and 
       
       
         
           
           
               
               
           
         
         wherein: 
         each of R and R′″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         two neighboring R′″s may be connected to form a ring; and 
         if at least one Rs is a hydrogen radical, all R′″s are not hydrogen radicals, and if at least one of R′″s is a hydrogen radical, all Rs are not hydrogen radical. 
       
     
     
       29. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the first metallocene compound is [A—O—(CH 2 ) a —C 5 H 4 ] 2 ZrCl 2  or [A—O—(CH 2 ) a —C 9 H 6 ]ZrCl 3 , wherein each a is an integer of 4 to 8, and each A is methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
     
     
       30. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the first metallocene compound is one of the following compounds: 
       
         
           
           
               
               
           
         
         wherein each a is an integer 4 to 8, and each A is methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
       
     
     
       31. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the second metallocene compound is a compound represented by the following Chemical Formula 2 or Chemical Formula 3: 
       
         
           
           
               
               
           
         
         wherein: 
         M is a group IV transition metal; 
         each of (C 5 R 3 ), (C 5 R 4 ) and (C 5 R 5 ) is a cyclopentadienyl; a cyclopentadienyl wherein two neighboring carbon atoms of C 5  are connected by a hydrocarbyl radical to form one or more C 4  to C 16  ring; or a substituted cyclopentadienyl ligand; 
         each of R 3 , R 4 , and R 5  is identical or different and a substituent selected from hydrogen radical, C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical; and at least one hydrogen radical comprised in the substituent of R 3 , R 4 , and R 5  is further substituted by a radical represented by the following Chemical Formula a, the following Chemical Formula b, the following Chemical Formula c, or the following Chemical Formula d; 
         each Q is identical or different halogen radical; C 1  to C 20  alkyl radical, alkenyl radical, aryl radical, alkylaryl radical, arylalkyl radical; or C 1  to C 20  alkylidene radical; 
         X is a bridge for binding two cyclopentadienyl ligands or a cyclopentadienyl ligand and JR 9   z−y  by a covalent bond, which is a radical having the formula of C m H 2m−1 , monoalkyl silicon, monoalkyl germanium, phosphine, or amine, wherein m is an integer of 1 to 4; 
         R 9  is a hydrogen radical, a C 1  to C 20  alkyl radical, an alkenyl radical, an aryl radical, an alkylaryl radical or an arylalkyl radical; 
         J is a group XV element or a group XVI element; 
         D is an oxygen or amine; 
         A is a hydrogen radical, a C 1  to C 20  alkyl radical, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, an alkylsilyl radical, an arylsilyl radical, methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl; and 
         a is an integer of 4 to 8: 
       
       
         
           
           
               
               
           
         
         wherein: 
         Z is an oxygen atom or a sulfur atom; 
         each of R and R′ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl; or arylalkenyl radical; and the two R′s may be connected to form a ring; 
         G is a C 1  to C 40  alkoxy, aryloxy, alkylthio, arylthio, phenyl or substituted phenyl, and may be connected to R′ to form a ring; 
         if Z is a sulfur atom, G should be alkoxy or aryloxy; and 
         if G is alkylthio, arylthio, phenyl or substituted phenyl, Z should be an oxygen atom; 
       
       
         
           
           
               
               
           
         
         wherein 
         Z is an oxygen atom or a sulfur atom, and at least one of the two Zs is an oxygen atom; 
         each of R and R″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         R and R″ may be connected to form a ring; and 
         unless both R″s are hydrogen radicals, they may be connected to form a ring; 
       
       
         
           
           
               
               
           
         
         wherein: 
         each of R and R′″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         two neighboring R′″s may be connected to form a ring; and 
         if at least one of Rs is a hydrogen radical, all R′″s are not hydrogen radicals, and if at least one of R′″s is a hydrogen radical, all Rs are not hydrogen radical; and 
       
       
         
           
           
               
               
           
         
         wherein: 
         Z is an oxygen, sulfur, nitrogen, phosphorus or arsenic atom; 
         each of R is identical or different hydrogen radical, C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         R″″ is a hydrogen radical or C 1  to C 40  alkyl, aryl, alkenyl, alkylaryl, alkylsilyl, arylsilyl, phenyl or substituted phenyl; and 
         n is 1 or 2, where if Z is oxygen or sulfur n is 1, and if Z is nitrogen, phosphorus or arsenic n is 2. 
       
     
     
       32. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the second metallocene compound is [A—D—(CH 2 ) a )(CH 3 )X(C 5 H 4 )(9-C 13 H 9 )]ZrCl 2  or [A—D—(CH 2 ) a )](CH 3 )X(C 5 Me 4 )(NCMe 3 )]TiCl 2 , wherein each a is an integer of 4 to 8, each X is C, CHCH or silicon, each D is an oxygen or amine, and each A is hydrogen, C 1  to C 20  alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkylsilyl, arylsilyl, methoxymethyl, t-butoxymethyl, tertahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
     
     
       33. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the second metallocene compound is one of the following compounds: 
       
         
           
           
               
               
           
         
         wherein each a is an integer of 4 to 8, each D is an oxygen or amine, and each A is a hydrogen radical, a C 1  to C 20  alkyl radical, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, an alkylsilyl radical, an arylsilyl radical, methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
       
     
     
       34. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the cocatalyst is a compound selected from a group consisting of compounds represented by the following Chemical Formula 4, Chemical Formula 5 and Chemical Formula 6:
   —[Al(R 6 )—O] n —  Chemical Formula 4 
 wherein: 
 R 6  is a C 1  to C 20  hydrocarbyl radical substituted by identical or different halogen radical, C 1  to C 20  hydrocarbyl radical or halogen; and 
 a is an integer larger than 2;
   M′(R 7 ) 3   Chemical Formula 5 
 
 wherein: 
 M′ is aluminum or boron; and 
 R 7  is a C 1  to C 20  hydrocarbyl radical substituted by identical or different halogen radical, C 1  to C 20  hydrocarbyl radical or halogen; and
   [L—H] + [M′E 4 ] −  or [L] + [M′E 4 ] −   Chemical Formula 6 
 
 wherein: 
 L is a neutral or cationic Lewis acid; 
 H is a hydrogen atom; 
 M′ is a group XIII element, such as aluminum and boron; and 
 E is a C 6  to C 40  aryl radical substituted by one or more C 1  to C 20  hydrocarbyl radicals containing a halogen radical, C 1  to C 20  hydrocarbyl, alkoxy, phenoxy radical, nitrogen, phosphorus, sulfur or oxygen atom, and the four Es may be identical or different. 
 
     
     
       35. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the support is dried at high temperature ranging from 300 to 1,000° C. and has highly reactive siloxane groups on the surface. 
     
     
       36. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the support is silica, silica-alumina or silica-magnesia. 
     
     
       37. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the support has 0.1 to 10 mmol/g of alcohol groups (—OH) on the surface. 
     
     
       38. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the supporting amount of the first metallocene compound and the second metallocene compound is 0.1 to 20 wt % of the total supported hybrid metallocene catalyst weight, based on the weight of group IV metals comprised in each compound. 
     
     
       39. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the supporting amount of the cocatalyst is 1 to 10,000 mol of the group XIII metal for 1 mol of the group IV metal comprised in the second metallocene compound. 
     
     
       40. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , wherein the supporting amount of the second metallocene compound is 0.01 to 100 mol for 1 mol of the first metallocene compound. 
     
     
       41. The method for preparing a supported hybrid metallocene catalyst according to  claim 26 , which further comprises a step of contacting the supported hybrid metallocene catalyst with an olefinic monomer to prepare a pre-polymerized catalyst. 
     
     
       42. A method for olefin polymerization comprising a step of polymerizing an olefinic monomer in the presence of a supported hybrid metallocene catalyst wherein at least two different metallocene compounds, which comprise a first metallocene compound whose ligand is supported to the support surface by chemical bonding, a second metallocene compound whose ligand is supported to a cocatalyst, which is chemically bonded to the support surface, by chemical bonding, a cocatalyst and a support, are supported on a single support. 
     
     
       43. The method for olefin polymerization according to  claim 42 , wherein the first metallocene compound is a catalyst for low molecular weight polyolefin polymerization and the second metallocene compound is a catalyst for high molecular weight polyolefin polymerization. 
     
     
       44. The method for olefin polymerization according to  claim 43 , wherein the low molecular weight polyolefin has a molecular weight ranging from 1,000 to 100,000, and the high molecular weight polyolefin has a molecular weight higher than that of the low molecular weight polyolefin, ranging from 10,000 to 1,000,000. 
     
     
       45. The method for olefin polymerization according to  claim 42 , wherein the first metallocene compound is supported on the support by a chemical bond of its ligand to the support surface; and the second metallocene compound is supported on the support by a chemical bond of its ligand to a cocatalyst chemically bonded to the support surface. 
     
     
       46. The method for olefin polymerization according to  claim 42 , wherein the supporting amount of the metallocene compounds is 0.1 to 20 wt % of the total supported hybrid metallocene catalyst weight, based on the weight of metals comprised in each metallocene compound. 
     
     
       47. The method for olefin polymerization according to  claim 42 , wherein the supporting amount of said at least one metallocene compound is 0.01 to 100 mol for 1 mol of the other metallocene compound. 
     
     
       48. The method for olefin polymerization according to  claim 42 , wherein a cocatalyst component for polyolefin polymerization is further supported on the supported hybrid metallocene catalyst. 
     
     
       49. The method for olefin polymerization according to  claim 48 , wherein the supporting amount of the cocatalyst is 1 to 10,000 mol for 1 mol of metals comprised in the metallocene compound. 
     
     
       50. A method for preparing polyolefin having a bimodal or broad molecular weight distribution, which comprises a step of polymerizing an olefinic monomer in the presence of the supported hybrid metallocene catalyst according to  claim 7 . 
     
     
       51. The method for preparing polyolefin according to  claim 50 , wherein the supported hybrid metallocene catalyst has been pre-polymerized by contact with an olefinic monomer. 
     
     
       52. The method for preparing polyolefin according to  claim 50 , wherein the polymerization is performed in a single reactor. 
     
     
       53. The method for preparing polyolefin according to  claim 50 , wherein the polymerization is performed by a slurry process or a gas phase process. 
     
     
       54. The method for preparing polyolefin according to  claim 50 , wherein the polymerization is performed at a temperature ranging from 25 to 500° C. 
     
     
       55. The method for preparing polyolefin according to  claim 50 , wherein the polymerization is performed at a pressure ranging from 1 to 100 Kgf/cm 2 . 
     
     
       56. The method for preparing polyolefin according to  claim 50 , wherein the supported hybrid metallocene catalyst is diluted in a C 5  to C 12  aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or hydrocarbon solvent substituted by a chlorine atom into a slurry, and then injected to an olefinic monomer. 
     
     
       57. The method for preparing polyolefin according to  claim 50 , wherein the olefinic monomer is selected from a group consisting of α-olefin, cyclic olefin, a dienic olefinic monomer and a trienic olefinic monomer. 
     
     
       58. The method for preparing polyolefin according to  claim 50 , wherein the polyolefin has a molecular weight distribution (Mw/Mn) ranging from 3 to 50. 
     
     
       59. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the first metallocene compound is a compound represented by the following Chemical Formula 1:
   (C 5 R 1 ) p (C 5 R 2 )MQ 3−p   Chemical Formula 1 
 wherein: 
 M is a group IV transition metal; 
 each of (C 5 R 1 ) and (C 5 R 2 ) is cyclopentadienyl; cyclopentadienyl wherein two neighboring carbon atoms of C 5  are connected by a hydrocarbyl radical to form one or more C 4  to C 16  rings; or a substituted cyclopentadienyl ligand; 
 each of R 1  and R 2  is identical or different and a substituent selected from hydrogen radical, C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical; and at least one hydrogen radical comprised in the substituent of R 1  and R 2  is further substituted by a radical represented by the following Chemical Formula a, the following Chemical Formula b, or the following Chemical Formula c; 
 Q is a halogen radical; a C 1  to C 20  alkyl radical, alkenyl radical, aryl radical, alkylaryl radical, arylalkyl radical; or a C 1  to C 20  alkylidene radical; and 
 P is 0 or 1: 
 
       
         
           
           
               
               
           
         
         wherein: 
         Z is an oxygen atom or a sulfur atom; 
         each of R and R′ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl; or arylalkenyl radical; and the two R′s may be connected to form a ring; 
         G is a C 1  to C 40  alkoxy, aryloxy, alkylthio, arylthio, phenyl or substituted phenyl, and may be connected to R′ to form a ring; 
         if Z is a sulfur atom, G should be alkoxy or aryloxy; and 
         if G is alkylthio, arylthio, phenyl or substituted phenyl, Z should be an oxygen atom; 
       
       
         
           
           
               
               
           
         
         wherein 
         Z is an oxygen atom or a sulfur atom, and at least one of the two Zs is an oxygen atom; 
         each of R and R″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         R and R″ may be connected to form a ring; and 
         unless both R″s are hydrogen radicals, they may be connected to form a ring; and 
       
       
         
           
           
               
               
           
         
         wherein: 
         each of R and R′″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         two neighboring R′″s may be connected to form a ring; and 
         if at least one of Rs is a hydrogen radical, all R′″s are not hydrogen radicals, and if at least one of R′″s is a hydrogen radical, all Rs are not hydrogen radical. 
       
     
     
       60. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the first metallocene compound is [A—O—(CH 2 ) a —C 5 H 4 ] 2 ZrCl 2  or [A—O—(CH 2 ) a —C 9 H 6 ]ZrCl 3 , wherein each a is an integer of 4 to 8, and each A is methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
     
     
       61. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the first metallocene compound is one of the following compounds: 
       
         
           
           
               
               
           
         
         wherein each a is an integer 4 to 8, and each A is methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
       
     
     
       62. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the second metallocene compound is a compound represented by the following Chemical Formula 2 or Chemical Formula 3: 
       
         
           
           
               
               
           
         
         wherein: 
         M is a group IV transition metal; 
         each of (C 5 R 3 ), (C 5 R 4 ) and (C 5 R 5 ) is a cyclopentadienyl; a cyclopentadienyl wherein two neighboring carbon atoms of C 5  are connected by a hydrocarbyl radical to form one or more C 4  to C 16  ring; or a substituted cyclopentadienyl ligand; 
         each of R 3 , R 4 , and R 5  is identical or different and a substituent selected from hydrogen radical, C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl, or arylalkenyl radical; and at least one hydrogen radical comprised in the substituent of R 3 , R 4 , and R 5  is further substituted by a radical represented by the following Chemical Formula a, the following Chemical Formula b, the following Chemical Formula c, or the following Chemical Formula d; 
         each Q is identical or different halogen radical; C 1  to C 20  alkyl radical, alkenyl radical, aryl radical, alkylaryl radical, arylalkyl radical; or C 1  to C 20  alkylidene radical; 
         X is a bridge for binding two cyclopentadienyl ligands or a cyclopentadienyl ligand and JR 9   z−y  by a covalent bond, which is a radical having the formula of C m H 2m−1 , monoalkyl silicon, monoalkyl germanium, phosphine, or amine, wherein m is an integer of 1 to 4; 
         R 9  is a hydrogen radical, a C 1  to C 20  alkyl radical, an alkenyl radical, an aryl radical, an alkylaryl radical or an arylalkyl radical; 
         J is a group XV element or a group XVI element; 
         D is an oxygen or amine; 
         A is a hydrogen radical, a C 1  to C 20  alkyl radical, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, an alkylsilyl radical, an arylsilyl radical, methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl; and 
         a is an integer of 4 to 8: 
       
       
         
           
           
               
               
           
         
         wherein: 
         Z is an oxygen atom or a sulfur atom; 
         each of R and R′ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl; or arylalkenyl radical; and the two R′s may be connected to form a ring; 
         G is a C 1  to C 40  alkoxy, aryloxy, alkylthio, arylthio, phenyl or substituted phenyl, and may be connected to R′ to form a ring; 
         if Z is a sulfur atom, G should be alkoxy or aryloxy; and 
         if G is alkylthio, arylthio, phenyl or substituted phenyl, Z should be an oxygen atom; 
       
       
         
           
           
               
               
           
         
         wherein 
         Z is an oxygen atom or a sulfur atom, and at least one of the two Zs is an oxygen atom; 
         each of R and R″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         R and R″ may be connected to form a ring; and 
         unless both R″s are hydrogen radicals, they may be connected to form a ring; 
       
       
         
           
           
               
               
           
         
         wherein: 
         each of R and R′″ is identical or different hydrogen radical; C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         two neighboring R′″s may be connected to form a ring; and 
         if at least one of Rs is a hydrogen radical, all R′″s are not hydrogen radicals, and if at least one of R′″s is a hydrogen radical, all Rs are not hydrogen radical; and 
       
       
         
           
           
               
               
           
         
         wherein: 
         Z is an oxygen, sulfur, nitrogen, phosphorus or arsenic atom; 
         each of R is identical or different hydrogen radical, C 1  to C 40  alkyl, cycloalkyl, aryl, alkenyl, alkylaryl, arylalkyl or arylalkenyl radical; 
         R″″ is a hydrogen radical or C 1  to C 40  alkyl, aryl, alkenyl, alkylaryl, alkylsilyl, arylsilyl, phenyl or substituted phenyl; and 
         n is 1 or 2, where if Z is oxygen or sulfur n is 1, and if Z is nitrogen, phosphorus or arsenic n is 2. 
       
     
     
       63. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the second metallocene compound is [(A—D—(CH 2 ) a )(CH 3 )X(C 5 H 4 )(9-C 13 H 9 )]ZrCl 2  or [(A—D—(CH 2 ) a )](CH 3 )X(C 5 Me 4 )(NCMe 3 )]TiCl 2 , wherein each a is an integer of 4 to 8, each X is C, CHCH or silicon, each D is an oxygen or amine, and each A is hydrogen, C 1  to C 20  alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkylsilyl, arylsilyl, methoxymethyl, t-butoxymethyl, tertahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
     
     
       64. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the second metallocene compound is one of the following compounds: 
       
         
           
           
               
               
           
         
         wherein each a is an integer of 4 to 8, each D is an oxygen or amine, and each A is a hydrogen radical, a C 1  to C 20  alkyl radical, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, an alkylsilyl radical, an arylsilyl radical, methoxymethyl, t-butoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 1-ethoxyethyl, 1-methyl-1-methoxyethyl or t-butyl. 
       
     
     
       65. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the cocatalyst is a compound selected from a group consisting of compounds represented by the following Chemical Formula 4, Chemical Formula 5 and Chemical Formula 6:
   —[Al(R 6 )—O] n —  Chemical Formula 4 
 wherein: 
 R 6  is a C 1  to C 20  hydrocarbyl radical substituted by identical or different halogen radical, C 1  to C 20  hydrocarbyl radical or halogen; and 
 a is an integer larger than 2;
   M′(R 7 ) 3   Chemical Formula 5 
 
 wherein: 
 M′ is aluminum or boron; and 
 R 7  is a C 1  to C 20  hydrocarbyl radical substituted by identical or different halogen radical, C 1  to C 20  hydrocarbyl radical or halogen; and
   [L—H] + [M′E 4 ] −  or [L] + [M′E 4 ] −   Chemical Formula 6 
 
 wherein: 
 L is a neutral or cationic Lewis acid; 
 H is a hydrogen atom; 
 M′ is a group XIII element, such as aluminum and boron; and 
 E is a C 6  to C 40  aryl radical substituted by one or more C 1  to C 20  hydrocarbyl radicals containing a halogen radical, C 1  to C 20  hydrocarbyl, alkoxy, phenoxy radical, nitrogen, phosphorus, sulfur or oxygen atom, and the four Es may be identical or different. 
 
     
     
       66. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the support is dried at high temperature ranging from 300 to 1,000° C. and has highly reactive siloxane groups on the surface. 
     
     
       67. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the support is silica, silica-alumina or silica-magnesia. 
     
     
       68. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the support has 0.1 to 10 mmol/g of alcohol groups (—OH) on the surface. 
     
     
       69. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the supporting amount of the first metallocene compound and the second metallocene compound is 0.1 to 20 wt % of the total supported hybrid metallocene catalyst weight, based on the weight of group IV metals comprised in each compound. 
     
     
       70. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the supporting amount of the cocatalyst is 1 to 10,000 mol of the group XIII metal for 1 mol of the group IV metal comprised in the second metallocene compound. 
     
     
       71. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , wherein the supporting amount of the second metallocene compound is 0.01 to 100 mol for 1 mol of the first metallocene compound. 
     
     
       72. The method for preparing a supported hybrid metallocene catalyst according to  claim 27 , which further comprises a step of contacting the supported hybrid metallocene catalyst with an olefinic monomer to prepare a pre-polymerized catalyst.